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| United States Patent |
5,013,485
|
|
Tsukuda
, et al.
|
May 7, 1991
|
Liquid detergent composition containing terpene and calcium or magnesium
salts
Abstract
A liquid detergent composition for household use is disclosed. It
comprises, as essential components, (A) 0.01-1.0% by weight of an anionic
surface active agent, (B) 0.01-1.0% by weight of a terpene-type
hydrocarbon solvent selected from monoterpenes and sesquiterpenes, and (C)
0.001-0.1% by weight of a water-soluble divalent metallic salt. The
composition has superior detergency, exhibits a minimum adverse effect on
surfaces which it contacts and a high degree of safety when in contact
with the human body, and does not require rinsing.
| Inventors:
|
Tsukuda; Kazunori (Utsunomiya, JP);
Toda; Masakazu (Utsunomiya, JP);
Saito; Masami (Ichikai, JP);
Tsumadori; Masaki (Utsunomiya, JP)
|
| Assignee:
|
Kao Corporation (Tokyo, JP)
|
| Appl. No.:
|
373278 |
| Filed:
|
June 28, 1989 |
Foreign Application Priority Data
| Jul 19, 1988[JP] | 63-177996 |
| Current U.S. Class: |
510/432; 510/181; 510/182; 510/424; 510/505 |
| Intern'l Class: |
C11D 001/12; C11D 003/04; C11D 003/18 |
| Field of Search: |
252/106,107,111,114,118,122,139,153,162,170,171,545,546,540,551,550,554
|
References Cited
U.S. Patent Documents
| 4414128 | Nov., 1983 | Goffinet | 252/111.
|
Primary Examiner: Willis; Prince E.
Assistant Examiner: McNally; John F.
Attorney, Agent or Firm: Oblon, Spivak, McClelland, Maier & Neustadt
Claims
What is claimed is:
1. A liquid detergent composition comprising as essential components:
(A) 0.01-1.0% by weight of an anionic surface active agent,
(B) 0.01-1.0% by weight of a terpene hydrocarbon solvent selected from
monoterpenes and sesqueterpenes; and
(C) 0.001-0.1% by weight of a water-soluble divalent metallic salt selected
from the group consisting of CaCl.sub.2, CaSO.sub.4 and MgSO.sub.4.
2. The liquid detergent composition of claim 1, wherein the anionic surface
active agent is selected from the group consisting of the linear or
branched alkyl C.sub.8 -C.sub.23 benzene sulfonates, long chain alkyl
C.sub.8 -C.sub.22 sulfonates, long chain olefin C.sub.8 -C.sub.22
sulfonates, long chain monoalkyl C.sub.8 -C.sub.22 sulfates,
polyoxyethylene (1-6 mol) long chain alkyl C.sub.8 -C.sub.22 ether
sulfates and polyoxyethylene (1-6 mols) alkyl C.sub.8 -C.sub.18
phenylether sulfates or mixtures thereof.
3. The liquid detergent composition of claim 1, wherein the anionic surface
active agent is present in from 0.1-0.5% by weight.
4. The liquid detergent composition of claim 1, wherein the terpene
hydrocarbon solvent is selected from the group consisting of D-limonene,
L-limonen, orange oil, lemon oil, .alpha.-terpineol, pine oil,
.alpha.-pinene, .beta.-pinene, myrcene, p-cymene, terpentine oil,
caryophyllene, cedrene, cedar oil, clover oil, and cananga oil or mixtures
thereof.
5. The liquid detergent composition of claim 1, wherein the terpene
hydrocarbon is present in from 0.1-0.5% by weight.
6. The liquid detergent composition of claim 1, wherein the counterion of
the anionic surface active agent is selected from the group consisting of
alkali metal ions, alkanolamine ions.
7. The liquid detergent composition of claim 1, wherein the anionic surface
active agent is a linear or branched alkyl benzene sulfonate.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a liquid detergent composition, and, in
particular, to a liquid detergent composition for household use having
superior detergency, as well as exhibiting a minimum adverse effect on
surfaces which it contacts, a high degree of safety when in contact with
the human body, and which does not require rinsing.
2. Description of the Background
In general, when a prolonged period of time elapses after a solid surface
gets soiled, washing becomes difficult because the soiling material
adheres strongly to the surface. For example, in the case where dirt
adhering to exhaust fan blades, walls in the kitchen area, glass,
refrigerator surfaces, and the like has accumulated over a long period of
time, this dirt changes to a highly viscous, oxidized form of degenerated
oils. In addition, difficult-to-clean, oily-type soiling, such as that
from hand stains, cigarette tars, and the like exists throughout the
household in locations other than the kitchen area.
Commonly known detergents for removing such oily-type soiling include those
containing a strong alkaline agent such as sodium hydroxide or the like,
as a major component, and those containing an organic amine, a
water-soluble organic solvent (such as ethylene glycol monoalkyl ether,
diethylene glycol monoalkyl ether, or the like), and a surface active
agent.
However, the former type presents a safety problem, especially with respect
to skin irritation, while the latter type gives rise to discomfort because
of having an offensive odor of the organic solvent.
Detergents containing monoterpenes and sesquiterpenes have been proposed as
detergents with a high degree of safety and without an offensive odor of
organic solvents (Japanese Patent Laid-open Nos. 14296/1986, 14297/1986,
and 164798/1987). Although they have high detergency performance, their
handling is sometimes cumbersome upon practical use. For example, they
must be diluted with water before use, or rinsed off with water after
being used in the original liquid form. This problem is caused by abrasive
powders contained in the detergent or surface active agents contained in
the emulsion type detergents.
SUMMARY OF THE INVENTION
The present inventors conducted extensive studies to provide, with due
consideration to the drawbacks of such conventional detergents, a liquid
detergent composition for household use having superior detergency,
exhibiting a minimum adverse effect on surfaces which it contacts, and a
high degree of safety when in contact with the human body, and which does
not require rinsing, and found that a liquid detergent composition which
comprises an anionic surface active agent, a terpene-type hydrocarbon
selected from monoterpenes and sesquiterpenes, and a water-soluble
divalent metal salt, did not require dilution prior to use, nor an
after-rinse, had a high degree of safety, and easily removed soiling.
Accordingly, an object of the present invention is to provide a liquid
detergent composition comprising as essential components:
(A) 0.01-1.0% by weight of an anionic surface active agents,
(B) 0.01-1.0% by weight of a terpene-type hydrocarbon solvent selected from
monoterpenes and sesquiterpenes, and
(C) 0.001-0.1% by weight of a water-soluble divalent metal salt.
Other objects, features and advantages of the invention will hereinafter
become more readily apparent from the following description.
DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS
Examples of the anionic surface active agent used as the component (A) in
the present invention include sulfonate-type anionic surface active agents
and sulfate-type anionic surface active agents commonly used in detergent
compositions. The sulfonate-type anionic surface active agents include
linear or branched alkyl (C.sub.8 -C.sub.23) benzene sulfonates, long
chain alkyl (C.sub.8 -C.sub.22) sulfonates, and long chain olefin (C.sub.8
-C.sub.22) sulfonates. Examples of sulfate-type anionic surface active
agents include long chain monoalkyl (C.sub.8 -C.sub.22) sulfates,
polyoxyethylene (1-6 mols) long chain alkyl (C.sub.8 -C.sub.22) ether
sulfates, polyoxyethylene (1-6 mols) alkyl (C.sub.8 -C.sub.18) phenylether
sulfates, and the like. As counter ions to these anionic surface active
agents, examples which can be given are alkali metal ions such as sodium,
potassium, and the like, and alkanolamine ions such as monoethanolamine,
diethanolamine, triethanolamine, and the like.
Among the above anionic surface active agents the sulfonate-type anionic
surface active agents are particularly desirable as the (A) component of
the present invention from the aspect of high resistance to hydrolysis. In
addition, linear or branched alkylbenzene sulfonates are desirable from
the aspect of high detergency.
The (A) component anionic surface active agents may be used individually or
as a mixture of two or more types in the composition of the present
invention.
The amount of the (A) component as a percentage by weight (hereinafter
referred to as wt %) of the total composition is in the range of 0.01 to
1.0 wt %; a particularly desirable amount is in the range of 0.1 to 0.5 wt
%. If the amount is less than 0.01 wt % of the mixture, the surface active
agent exhibits insufficient emulsifying and dispersion action and the
solubilizing activity is inadequate; if greater than 1.0 wt %, it leaves
wiping traces on the surface of the washed object after wiping, which
needs an undesirable rinsing step.
The component (B) of the composition of the present invention is a
terpene-type hydrocarbon solvent selected from monoterpenes and
sesquiterpenes. Examples of monoterpene-type hydrocarbon solvents are
D-limonene and L-limonene which are contained in orange oil, lemon oil, or
the like, .alpha.-terpineol contained in pine oil or the like, and
.alpha.-pinene, .beta.-pinene, myrcene, and p-cymene contained in
turpentine oil or the like. Examples of sesquiterpene-type hydrocarbon
solvents which can be given are caryophyllene, cedrene, and the like,
which are contained in substantial quantities in cedar oil, clover oil,
cananga oil, and the like.
The (B) component which is a terpene-type hydrocarbon solvent selected from
monoterpenes and sesquiterpenes may be used individually or as a mixture
of two or more types in the composition of the present invention. In
addition, it is possible to incorporate their starting materials of orange
oil, turpentine oil, or pine oil as they are into the composition of the
present invention.
A desirable amount of the (B) component as a percentage of the total
composition is in the range of 0.01 to 1.0 wt %; a particularly desirable
amount is in the range of 0.1 to 0.5 wt %. If the amount is less than 0.01
wt % of the composition, action as a solvent cannot be expected; if
greater than 1.0 wt %, a large amount of a surface active agent is
necessary to ensure stable solubilization of the compound. Because
remnants remain on the surface of the washed object they must be rinsed
and wiped a second time, which is undesirable.
Water-soluble divalent metal salts which are suitable as the component (C)
of the composition of the present invention are, for example, calcium
salts and magnesium salts. Of the calcium salts, the chloride and the
sulfate are particularly desirable; for the magnesium salts, the sulfate
is best used.
A desirable amount of the (C) component in a percentage of the total
composition is in the range of 0.001 to 0.1 wt %. The HLB value of the
component (A) of the present invention can be freely adjusted
corresponding to the amount of the component (C) added. Addition of the
component (C) also assists to solubilize the component (B).
In addition, as required, components other than the essential components
(A), (B), and (C) can be added to the liquid detergent composition of the
present invention. These optional components include nonionic surface
active agents, alkaline agents, dispersing agents, solvents, acids,
perfumes, dyes, pigments, preservatives, germicides, and the like.
Other features of the invention will become apparent in the course of the
following description of the exemplary embodiments which are given for
illustration of the invention and are not intended to be limiting thereof.
EXAMPLES
Example 1
Detergent compositions listed in the following Table 1 were prepared and
actually used to wash a household window glass. The detergency, wiping
traces, and solvent odor were then evaluated.
The object window glass was sprayed with 1 cc of a liquid detergent using a
commercial sprayer, and wiped with a dry towel. Sensory evaluations were
then carried out, using the following evaluation criteria.
Evaluation Criteria
Detergency
O: 80% of soiling is removed
F: 20 to 50% of soiling is removed
X: Almost no soiling removed
Wiping traces
O: Second wiping not necessary
F: Slight wiping traces remaining
X: Considerable wiping traces observed
Solvent odor
O: No objectionable odor detected
F: Slight objectionable odor
X: Objectionable odor noted
The results are shown in Table 1.
TABLE 1
__________________________________________________________________________
(wt %)
Components 1 2 3 4 5 6* 7*
__________________________________________________________________________
Sodium alkylbenzene
0.5 0.5 0.3 0.3 1.5 0.2 0.3
sulfonate(1)
Polyoxyethylenealkyl-
-- -- -- 0.2 -- 0.1 --
ether(2)
D-limonene -- -- 0.3 -- 0.5 0.3 --
.alpha.-Pinene
-- -- -- 0.5 -- -- 0.5
Ethyl cellosolve
1.0 -- -- -- -- -- --
Butyl carbitol
-- 1.0 -- -- -- -- --
Calcium chloride
-- -- -- -- 0.01
0.01
0.01
Ion exchanged water
Balance
Balance
Balance
Balance
Balance
Balance
Balance
Detergency O O F F O O O
Wiping traces
O F F F X O O
Solvent odor
X F O O O O O
__________________________________________________________________________
*Compositions of the present invention
(1) An average cabon number in alkyl chain: C.sub.12
(2) An average cabon number in alkyl chain: C.sub.12, An average ethylene
oxide addition mols: 6
Example 2
Detergent compositions listed in the following Table 2 were prepared, and
the detergency and wiping traces were evaluated using soiled models.
Soiled models used were 3 cm.times.8 cm glass plates to which cigarette
tars were adhered. The glass plates were immersed in test solutions for 2
minutes and the elimination of the soiling was evaluated to determine the
detergency according to the following criteria. The glass plates were
wiped with dry towel and the completeness after drying was sensorially
evaluated according to the following criteria to determine wiping traces.
Detergency
O: 80% of soiling is removed
F: 20 to 50% of soiling is removed
X: Almost no soiling removed
Wiping traces
O: Second wiping not necessary
F: Slight wiping traces remaining
X: Considerable wiping traces observed
Results are shown in Table 2.
TABLE 2
__________________________________________________________________________
(wt %)
Components 8* 9* 10* 11* 12* 13 14 15
__________________________________________________________________________
Sodium alkylbenzene
0.3 0.3 0.3 0.3 0.5 0.3 0.3 2.5
solfonate(1)
Polyoxyethylenealkyl-
0.1 0.1 0.1 0.1 0.5 0.1 0.1 2.5
ether(2)
Orange oil (Major
0.5 -- -- -- 1.0 -- -- 10.0
component: D-limonene)
Turpentine oil (Major
-- 0.5 -- -- -- -- -- --
component: .alpha., .beta.-pinene)
Cananga oil (Major
-- -- 0.5 -- -- -- -- --
component: .alpha.,
.beta.-caryophyllene)
.alpha.-terpineol
-- -- -- 0.5 -- -- -- --
Butyl carbitol
-- -- -- -- -- 3.0 -- --
Ethanol -- -- -- -- -- -- 10.0 --
Diethanolamine
0.5 0.5 0.5 0.5 0.1 0.5 0.5 0.1
Calcium chloride
0.01
0.01
0.01
0.01
0.01
-- -- --
Ion exchanged water
Balance
Balance
Balance
Balance
Balance
Balance
Balance
Balance
Detergency O O O O O O F O
Wiping traces
O O O O O F O X
__________________________________________________________________________
*Compositions of the present invention
(1) An average cabon number in alkyl chain: C.sub.12
(2) An average cabon number in alkyl chain: C.sub.12, An average ethylene
oxide addition mols: 6
Obviously, numerous modifications and variations of the present invention
are possible in light of the above teachings. It is therefore to be
understood that within the scope of the appended claims, the invention may
be practiced otherwise than as specifically described herein.
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